Curing agent for epoxy resins

ABSTRACT

The present disclosure provides a curing agent comprising a polyetheramine, a tertiary amine substantially free of an aromatic tertiary amine and glycerin. The curing agent may be combined with an epoxy resin to form a curable composition which is capable of being applied to a substrate and cured to form a cured article.

CROSS-REFERENCE TO RELATED APPLICATION

The present application claims priority to U.S. Provisional PatentApplication Ser. No. 62/455,018, filed Feb. 6, 2017, the entire contentsof which is hereby expressly incorporated herein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

FIELD OF THE INVENTION

The present disclosure generally relates to a curing agent comprising apolyetheramine, a tertiary amine and glycerin. The curing agent may becombined with an epoxy resin to form a curable composition which can beapplied to a substrate and cured to form a cured article.

BACKGROUND OF THE INVENTION

Curable compositions based on epoxy resins and various curing agents areused in the industry on a large scale to produce cured epoxy resins. Astypical representative examples of curing agents, there are, forexample, diethylenetriamine, triethylenetetramine, isophoronediamine,diaminodiphenylmethane, diaminodiphenylsulfone, polyamides,dicyandiamide, hexahydrophthalic anhydride, methyltetrahydrophthalicanhydride, methyl nadic anhydride, imidazoles, and amine complexes ofboron trifluoride.

Polyetheramines have also been used in the curing of epoxy resins toprovide cured articles that exhibit superior physical properties in manyapplications, such as composites, castings, adhesives, etc. (see, e.g.,WO 2016/089663; U.S. Pat. Nos. 9,012,020; 8,399,577; US Pat. Appl. Pub.No. 2013/0012669; U.S. Pat. Nos. 7,816,481; and 3,654,370, each of whichis hereby incorporated by reference to the extent that they do notcontradict the present disclosure). However, the cost of suchpolyetheramines may be considered too high for use in some applications(e.g. floor coatings) in which the cured article exhibits physicalproperties much better than generally required. Accordingly, it would bedesirable to develop new polyetheramine-based curing agents having areduced usage level of polyetheramine thereby reducing raw material costyet are still effective in curing epoxy resins to produce cured articleshaving acceptable physical and thermal properties.

SUMMARY OF THE INVENTION

The present disclosure generally provides a curing agent comprising (i)a polyetheramine; (ii) a tertiary amine substantially free of anaromatic tertiary amine; and (iii) glycerin.

In other aspects, there is provided a curable composition comprising thecuring agent of the present disclosure and an epoxy resin.

In still other aspects, there is provided a cured article obtained byapplying the curable composition to a substrate and curing the curablecomposition.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure generally provides a curing agent comprising (i)a polyetheramine selected from a polyether monoamine, a polyetherdiamine, a polyether triamine, a multifunctional polyetheramine and amixture thereof; (ii) a tertiary amine substantially free of an aromatictertiary amine; and (iii) glycerin. It has been surprisingly found thatthis combination of components not only produces a curing agent at amuch lower cost than that for state of the art polyetheramine-basedcuring agents, but can also rapidly cure an epoxy resin to provide acured article having an excellent balance of physical and thermalproperties.

The following terms shall have the following meanings:

As used herein, the term “curing” or “cure” refers to the hardening ofan epoxy resin by chemical cross-linking. The term “curable” means thatthe composition is capable of being subjected to conditions which willrender the composition to a cured or thermoset state or condition.

The term “alkyl” means a straight or branched-chain alkyl group such as,for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyland pentyl.

The term “aromatic tertiary amine” refers to a tertiary amine containingan aryl moiety, with the term “aryl” referring to a substituted orunsubstituted aromatic carbocyclic radical having 6 to 14 carbon atoms.

The term “cycloalkyl” means a cycloaliphatic group containing from 3 to10 carbon atoms including, but not limited to, cyclopropyl, cyclobutyl,cyclopentyl and cyclohexyl.

The term “heterocycloalkyl” includes heterocycloalkyl groups containing3 to 6 carbon atoms and one or two oxygen, sulphur or nitrogen atoms.Particular examples of such groups include azetidinyl, pyrrolidinyl,piperidinyl, homopiperidinyl, piperazinyl, homopiperazinyl, morpholinyland thiomorpholinyl groups.

The term “substantially free” means, when used with reference to thesubstantial absence of a material in a formulation, that such a materialis not present, or if at all, as an incidental impurity or by-product.In other words, the material does not affect the properties of theformulation.

The term “comprising” and derivatives thereof are not intended toexclude the presence of any additional component, step or procedure,whether or not the same is disclosed herein. In order to avoid anydoubt, all compositions claimed herein through use of the term“comprising” may include any additional additive or compound, unlessstated to the contrary. In contrast, the term, “consisting essentiallyof” if appearing herein, excludes from the scope of any succeedingrecitation any other component, step or procedure, excepting those thatare not essential to operability and the term “consisting of”, if used,excludes any component, step or procedure not specifically delineated orlisted. The term “or”, unless stated otherwise, refers to the listedmembers individually as well as in any combination.

The articles “a” and “an” are used herein to refer to one or more thanone (i.e. to at least one) of the grammatical object of the article. Byway of example, “an epoxy resin” means one epoxy resin or more than oneepoxy resin.

The phrases “in one aspect”, “according to one aspect” and the likegenerally mean the particular feature, structure, or characteristicfollowing the phrase is included in at least one aspect of the presentdisclosure, and may be included in more than one aspect of the presentdisclosure. Importantly, such phases do not necessarily refer to thesame aspect.

If the specification states a component or feature “may”, “can”,“could”, or “might” be included or have a characteristic, thatparticular component or feature is not required to be included or havethe characteristic.

Curing Agent

According to one aspect, the curing agent of the present disclosureincludes: (i) a polyetheramine selected from the group consisting of: apolyether monoamine; a polyether diamine; a polyether triamine; amultifunctional polyetheramine and a mixture thereof; (ii) a tertiaryamine substantially free of an aromatic tertiary amine; and (iii)glycerin.

In one aspect, the polyetheramine is a polyether monoamine having theformula (1) or (1a):

where R is hydrogen, methyl or ethyl, and

a and b independently are integers from about 1 to about 150; or

where Y is hydrogen, methyl or ethyl,

Z is a C₁-C₄₀ alkyl group or a C₁-C₄₀ alkyl phenol group and

w is an integer from about 1 to about 100.

In still another aspect, the polyetheramine is a polyether monoaminehaving the formula (2) or (2a):

where Me is methyl and Et is ethyl.

Commercially available polyether monoamines include the JEFFAMINE®M-series and XTJ-series amines, including, but not limited to,JEFFAMINE® M-600, M-1000, M-2005, M-2070, XTJ-435 and XTJ-436 amines,available from Huntsman Petrochemical LLC.

In yet another aspect, the polyetheramine is a polyether diamine havingthe formula (3), (4) or (5):

where c is an integer from about 2 to about 100,

H is hydrogen, Me is methyl, Et is ethyl,

where H is hydrogen, Me is methyl, Et is ethyl,

e is an integer from about 2 to about 40, and

d and f independently are integers from about 1 to about 10; or

where g is an integer from about 2 to about 3.

Commercially available polyether diamines include the JEFFAMINE® D, EDand EDR amines, including, but not limited to, JEFFAMINE® D-230, D-400,D-2000, D-4000, ED-600, ED-900, ED-20003, EDR-148 and EDR-176 amines,available from Huntsman Petrochemical LLC.

In still yet another aspect, the polyetheramine is a polyether triaminehaving the formula (6):

where R₁ is hydrogen, methyl or ethyl,

H is hydrogen, Me is methyl, Et is ethyl,

n is an integer of 0 or 1, and

h, i and j independently are integers from about 1 to about 100.

Commercially available polyether triamines include the JEFFAMINE®T-series amines, including, but not limited to, JEFFAMINE® T-403, T-3000and T-5000 amines, available from Huntsman Petrochemical LLC.

In another aspect, the polyetheramine is a multifunctionalpolyetheramine. The multifunctional polyetheramine may be a polyetherdi- or triamine, such as those described herein, having at least one ofthe hydrogens of the amine groups replaced by a hydroxyl group. Forexample, the multifunctional polyetheramine may have the formula (7)

where each R₄ and R₅ are independently hydrogen or a hydroxyl group,with the proviso that at least one of R₄ is a hydrogen and at least oneof R₅ is a hydroxyl group,

H is hydrogen, Me is methyl and Et is ethyl.

In one particular aspect, the polyetheramine is selected from the groupconsisting of a polyether monoamine, a polyether diamine and a mixturethereof. In still another particular aspect, the polyetheramine is apolyether diamine.

According to another aspect, the curing agent includes at least about65% by weight of a polyetheramine, where the % by weight is based on thetotal weight of the curing agent. In another aspect, the curing agentincludes at least about 70% by weight of the polyetheramine, or at leastabout 75% by weight of the polyetheramine, where the % by weight isbased on the total weight of the curing agent. In still yet anotheraspect, the curing agent includes the polyetheramine in an amount of atleast about 80% by weight, or at least about 81% by weight, or at leastabout 82% by weight, or at least about 83% by weight, or at least about84% by weight, or at least about 85% by weight, where the % by weight isbased on the total weight of the curing agent.

In a further aspect, the curing agent includes from about 65% by weightto about 95% by weight of the polyetheramine, where the % by weight isbased on the total weight of the curing agent. In another aspect, thecuring agent includes from about 70% by weight to about 90% by weight ofthe polyetheramine, where the % by weight is based on the total weightof the curing agent. In still another aspect, the curing agent includesfrom about 75% by weight to about 85% by weight of the polyetheramine,where the % by weight is based on the total weight of the curing agent.

The curing agent also includes a tertiary amine substantially free of anaromatic tertiary amine. In one aspect, the tertiary amine is a compoundhaving the formula NR₇R₈R₉ where: (a) R₇, R₈ and R₉ independently areC₁-C₁₀ alkyl groups; or (b) R₇ and R₈ are joined as a heterocycloalkylresidue and R₉ is a C₁-C₁₀ alkyl group; or (c) R₇ and R₈ independentlyare C₁-C₁₀ alkyl groups and R₉ is a cycloalkyl group.

Exemplary tertiary amines include, but are not limited to,trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine,tri-iso-propylamine, tri-iso-butylamine, dimethylaminocyclohexane,diethylaminocyclohexane, dimethylaminocyclopentane,diethylaminocyclopentane, N-methylmorpholine, N—N-methylpyrrolidine,N-ethylpyrrolidine, N-n-propylpyrrolidine, N-iso-propylpyrrolidine,N-methylpiperidine, N-ethylpiperidine, N-n-propylpiperidine,N-iso-propylpiperidine, N,N′-dimethylpiperazine, N,N′-diethylpiperazine,N,N′-dipropylpiperazine, and mixtures thereof. In one particular aspect,the tertiary amine is trimethylamine, triethylamine, tri-n-propylamine,tri-iso-propylamine, tri-n-butylamine, dimethylaminocyclohexane orN-methylmorpholine. In another aspect, the tertiary amine isdimethylaminocyclohexane or N-methylmorpholine.

In one aspect, the curing agent may include less than about 10% byweight of the tertiary amine, where the % by weight is based on thetotal weight of the curing agent. In another aspect, the curing agentincludes less than about 8% by weight of the tertiary amine, or lessthan about 7.5% by weight of the tertiary amine, where the % by weightis based on the total weight of the curing agent. In still yet anotheraspect, the curing agent includes the tertiary amine in amount of lessthan about 5% by weight, or less than about 4% by weight, or less thanabout 3% by weight, or less than about 2.5% by weight, or less thanabout 2% by weight, or at less than about 1% by weight, where the % byweight is based on the total weight of the curing agent.

In still another aspect, the curing agent includes from about 0.1% byweight to about 10% by weight of the tertiary amine, where the % byweight is based on the total weight of the curing agent. In anotheraspect, the curing agent includes from about 0.5% by weight to about 5%by weight of the tertiary amine, where the % by weight is based on thetotal weight of the curing agent. In still another aspect, the curingagent includes from about 1% by weight to about 3% by weight of thetertiary amine, where the % by weight is based on the total weight ofthe curing agent.

The curing agent also includes glycerin. In one aspect, the curing agentincludes less than about 30% by weight of glycerin, where the % byweight is based on the total weight of the curing agent. In anotheraspect, the curing agent includes less than about 25% by weight ofglycerin, or at less than about 20% by weight of glycerin, where the %by weight is based on the total weight of the curing agent. In still yetanother aspect, the curing agent includes glycerin in an amount of lessthan about 15% by weight, or less than about 14% by weight, or less thanabout 13% by weight, or less than about 12% by weight, or less thanabout 11% by weight, or less than about 10% by weight, where the % byweight is based on the total weight of the curing agent.

In yet another aspect, the curing agent includes from about 1% by weightto about 25% by weight of glycerin, where the % by weight is based onthe total weight of the curing agent. In another aspect, the curingagent includes from about 5% by weight to about 20% by weight ofglycerin, where the % by weight is based on the total weight of thecuring agent. In still another aspect, the curing agent includes fromabout 10% by weight to about 15% by weight of glycerin, where the % byweight is based on the total weight of the curing agent.

Curable Composition

According to another aspect, there is provided a curable compositionthat includes: (i) an epoxy resin; and (ii) the curing agent of thepresent disclosure comprising a polyetheramine, a tertiary aminesubstantially free of an aromatic tertiary amine and glycerin asdescribed above.

In general, any epoxy-containing compound is suitable for use as theepoxy resin in the present disclosure, such as the epoxy-containingcompounds disclosed in U.S. Pat. No. 5,476,748 which is incorporatedherein by reference. The epoxy resin may be solid or liquid. In oneembodiment, the epoxy resin is selected from the group consisting of: apolyglycidyl epoxy compound; a non-glycidyl epoxy compound; an epoxycresol novolac compound; an epoxy phenol novolac compound; and a mixturethereof.

The polyglycidyl epoxy compound may be a polyglycidyl ether,poly(β-methylglycidyl) ether, polyglycidyl ester orpoly(β-methylglycidyl) ester. The synthesis and examples of polyglycidylethers, poly(β-methylglycidyl) ethers, polyglycidyl esters andpoly(β-methylglycidyl) esters are disclosed in U.S. Pat. No. 5,972,563,which is incorporated herein by reference. For example, ethers may beobtained by reacting a compound having at least one free alcoholichydroxyl group and/or phenolic hydroxyl group with a suitablysubstituted epichlorohydrin under alkaline conditions or in the presenceof an acidic catalyst followed by alkali treatment. The alcohols may be,for example, acyclic alcohols, such as ethylene glycol, diethyleneglycol and higher poly(oxyethylene) glycols, propane-1,2-diol, orpoly(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol,poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol,hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane,bistrimethylolpropane, pentaerythritol and sorbitol. Suitable glycidylethers may also be obtained, however, from cycloaliphatic alcohols, suchas 1,3- or 1,4-dihydroxycyclohexane, bis(4-hydroxycyclo-hexyl)methane,2,2-bis(4-hydroxycyclohexyl)propane or1,1-bis(hydroxymethyl)cyclohex-3-ene, or they may possess aromaticrings, such as N,N-bis(2-hydroxyethyl)aniline orp,p′-bis(2-hydroxyethylamino)diphenylmethane.

Particularly important representatives of polyglycidyl ethers orpoly((3-methylglycidyl)ethers are based on monocyclic phenols, forexample, on resorcinol or hydroquinone, on polycyclic phenols, forexample, on bis(4-hydroxyphenyl)methane (Bisphenol F),2,2-bis(4-hydroxyphenyl)propane (Bisphenol A),bis(4-hydroxyphenyl)sulfone (Bisphenol S), alkoxylated Bisphenol A, F orS, triol extended Bisphenol A, F or S, brominated Bisphenol A, F or S,hydrogenated Bisphenol A, F or S, glycidyl ethers of phenols and phenolswith pendant groups or chains, on condensation products, obtained underacidic conditions, of phenols or cresols with formaldehyde, such asphenol novolaks and cresol novolaks, or on siloxane diglycidyls.

Polyglycidyl esters and poly(β-methylglycidyl)esters may be produced byreacting epichlorohydrin or glycerol dichlorohydrin or3-methylepichlorohydrin with a polycarboxylic acid compound. Thereaction is expediently carried out in the presence of bases. Thepolycarboxylic acid compounds may be, for example, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid ordimerized or trimerized linoleic acid. Likewise, however, it is alsopossible to employ cycloaliphatic polycarboxylic acids, for exampletetrahydrophthalic acid, 4-methyltetrahydrophthalic acid,hexahydrophthalic acid or 4-methylhexahydrophthalic acid. It is alsopossible to use aromatic polycarboxylic acids such as, for example,phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid,or else carboxyl-terminated adducts, for example of trimellitic acid andpolyols, for example glycerol or 2,2-bis(4-hydroxycyclohexyl)propane,may be used.

In another aspect, the epoxy resin is a non-glycidyl epoxy compound.Non-glycidyl epoxy compounds may be linear, branched, or cyclic instructure. For example, there may be included one or more epoxidecompounds in which the epoxide groups form part of an alicyclic orheterocyclic ring system. Others include an epoxy-containing compoundwith at least one epoxycyclohexyl group that is bonded directly orindirectly to a group containing at least one silicon atom. Examples aredisclosed in U.S. Pat. No. 5,639,413, which is incorporated herein byreference. Still others include epoxides which contain one or morecyclohexene oxide groups and epoxides which contain one or morecyclopentene oxide groups.

Particular examples of non-glycidyl epoxy compound's include thefollowing difunctional non-glycidyl epoxide compounds in which theepoxide groups form part of an alicyclic or heterocyclic ring system:bis(2,3-epoxycyclopentyl)ether, 1,2-bis(2,3-epoxycyclopentyloxy)ethane,3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexanecarboxylate,3,4-epoxy-6-methyl-cyclohexylmethyl3,4-epoxy-6-methylcyclohexanecarboxylate,di(3,4-epoxycyclohexylmethyl)hexanedioate,di(3,4-epoxy-6-methylcyclohexylmethyl) hexanedioate,ethylenebis(3,4-epoxycyclohexanecarboxylate), ethanedioldi(3,4-epoxycyclohexylmethyl.

In some particular aspects, the difunctional non-glycidyl epoxycompounds include cycloaliphatic difunctional non-glycidyl epoxies, suchas 3,4-epoxycyclohexyl-methyl 3′,4′-epoxycyclohexanecarboxylate and2,2′-bis-(3,4-epoxy-cyclohexyl)-propane, with the former being mostpreferred.

In yet another aspect, the epoxy resin is a poly(N-glycidyl) compound orpoly(S-glycidyl) compound. Poly(N-glycidyl) compounds are obtainable,for example, by dehydrochlorination of the reaction products ofepichlorohydrin with amines containing at least two amine hydrogenatoms. These amines may be, for example, n-butylamine, aniline,toluidine, m-xylylenediamine, bis(4-aminophenyl)methane orbis(4-methylaminophenyl)methane. Other examples of poly(N-glycidyl)compounds include N,N′-diglycidyl derivatives of cycloalkyleneureas,such as ethyleneurea or 1,3-propyleneurea, and N,N′-diglycidylderivatives of hydantoins, such as of 5,5-dimethylhydantoin. Examples ofpoly(S-glycidyl) compounds are di-S-glycidyl derivatives derived fromdithiols, for example ethane-1,2-dithiol orbis(4-mercaptomethylphenyl)ether.

It is also possible to employ epoxy resins in which the 1,2-epoxidegroups are attached to different heteroatoms or functional groups.Examples include the N,N,O-triglycidyl derivative of 4-aminophenol, theglycidyl ether/glycidyl ester of salicylic acid,N-glycidyl-N′-(2-glycidyloxypropyl)-5,5-dimethylhydantoin or2-glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylhydantoin-3-yl)propane.

Other epoxide derivatives may also be employed, such as vinylcyclohexene dioxide, limonene dioxide, limonene monoxide, vinylcyclohexene monoxide, 3,4-epoxycyclohexlmethyl acrylate,3,4-epoxy-6-methyl cyclohexylmethyl 9,10-epoxystearate, and1,2-bis(2,3-epoxy-2-methylpropoxy)ethane.

Additionally, the epoxy resin may be a pre-reacted adduct of an epoxyresin, such as those mentioned above, with compounds having a freehydrogen that is reactive with an epoxy group. Typically, such reactivehydrogens are found in carboxylic acid groups, aromatic hydroxyl groups,amino groups, and sulfhydryl groups.

The amount of epoxy resin used in the curable composition may depend onthe targeted molecular weight and epoxy functionality. In some aspects,the curable composition may include the epoxy resin in an amount of fromabout 30% by weight to about 85% by weight, where the % by weight isbased on the total weight of the curable composition. In other aspects,the curable composition may include the epoxy resin in an amount fromabout 40% by weight to about 85% by weight, or from about 45% by weightto about 80% by weight, where the % by weight is based on the totalweight of the curable composition.

In another aspect, the curable composition contains the curing agent ofthe present disclosure described above. In some aspects, the curablecomposition may include the curing agent in an amount of at least about5% by weight, or at least 10% by weight or at least 15% by weight or atleast 20% by weight, based on the total weight of the curablecomposition.

In yet another aspect, in addition to the epoxy resin and curing agentof the present disclosure, the curable composition may also contain oneor more other additives which are useful for their intended uses. Forexample, the optional additives useful in the curable composition mayinclude, but are not limited to, diluents (1,4-butanediol diglycidylether (BDDGE), 1,6 hexanediol diglycidyl ether (HDDGE), cresoldiglycidyl ether (CGE), C12-14 alkyl glycidyl ether (AGE), trimethylolpropane triglycidyl ether (TMPTGE)), inert fillers, reinforced fibers(carbon fiber, glass fiber, aramid fiber, boron fiber, silicon carbidefiber), stabilizers, surfactants, flow modifiers, pigments or dyes,release agents, matting agents, degassing agents, flame retardants(e.g., inorganic flame retardants, halogenated flame retardants, andnon-halogenated flame retardants such as phosphorus-containingmaterials), toughening agents (for e.g. carboxyl terminated liquidbutadiene acrylonitrile rubber (CTBN), acrylic terminated liquidbutadiene acrylonitrile rubber (ATBN), epoxy terminated liquid butadieneacrylonitrile rubber (ETBN), liquid epoxy resin (LER) adducts ofelastomers and preformed core-shell rubbers), curing initiators, curinginhibitors, wetting agents, processing aids, fluorescent compounds, UVstabilizers, antioxidants, impact modifiers and mixtures thereof.

When present, the amount of additives included in the curablecomposition may be at least about 0.5% by weight, or at least 2% byweight, or at least 5% by weight or at least 10% by weight, based on thetotal weight of the curable composition.

Further, the curable compositions within the scope of the presentdisclosure can be solventless, also referred to as solvent-free.Alternatively, the curable compositions of the present disclosure canfurther comprise at least one organic or aqueous solvent. Often, suchsolvent or mixture of solvents is chosen to give a specific evaporationrate profile for the curable composition while maintaining solubility ofthe components of the curable composition.

Examples of solvents which may be employed herein include, but are notlimited to, aliphatic hydrocarbons, aromatic hydrocarbons, glycolethers, amides, sulfoxides, sulfones, and mixtures thereof. Particularsolvents may include, for example, hexane, heptane, octane, nonane,decane, toluene, xylene, ethylene glycol methyl ether, ethylene glycolethyl ether, ethylene glycol n-butyl ether, ethylene glycol phenylether, propylene glycol methyl ether, propylene glycol phenyl ether,tripropylene glycol methyl ether, diethylene glycol methyl ether,diethylene glycol ethyl ether, diethylene glycol n-butyl ether,diethylene glycol phenyl ether, butylene glycol methyl ether,N,N-dimethylformamide, N-methylpyrolidinone, N,N-dimethylacetamide,dimethylsulfoxide, sulfolane and mixtures thereof.

In some aspects, the solvent may be included in the curable compositionin amounts from about 5% by weight to about 95% by weight, where the %by weight is based on the total weight of the curable composition andsolvent. In other aspects, the solvent may be used in amounts from about10% by weight to about 60% by weight, or from about 20% by weight toabout 40% by weight, where the % by weight is based upon the totalweight of the curable composition and solvent.

Formulating the Curable Composition

The curable composition may be prepared by stirring and mixing thecomponents in a state where the components are heated if needed, withoutparticular limitation. The curable composition of the present disclosuremay be a multi-package type (for e.g., 2-package type) composition whereat least two of the components of the curable composition are preparedseparately and packaged in separate containers (or vessels) and thecurable composition is obtained by mixing the two or more separatelyprepared components (for e.g., Part A is the epoxy resin and Part B isthe curing agent) at a predetermined ratio before use. Thestirring/mixing method is not particularly limited. For example, therecan be used a known or customary stirring/mixing unit such as a mixer(e.g., a dissolver, a homogenizer or a static mixer), a kneader, a roll,a bead mill, or a planetary stirring apparatus. The mixture afterstirring and mixing may be subjected to defoam in a vacuum.

In another aspect, the curable composition of the present disclosure is1-pot type composition achieved by admixing in a vessel the componentsincluding the epoxy resin and the curing agent of the present disclosureand then allowing the components to formulate into a curablecomposition. There is no criticality to the order of mixture, i.e., thecomponents may be admixed in any order to provide the curablecomposition of the present disclosure. Any of the above-mentionedoptional additives may also be added.

In one aspect, the epoxy resin and curing agent are combined so that theratio of the number of the equivalents of reactive amine hydrogens inthe curing agent to the number of the equivalents of epoxides present inthe curable composition ranges from about 0.2 to about 1.3, or fromabout 0.4 to about 1, or even from about 0.4 to about 0.9, or still evenfrom about 0.5 to about 0.85, and still even from about 0.6 to about 0.8and in some cases from about 0.65 to about 0.75. In still other aspects,the epoxy resin and curing agent are combined at a weight ratio of epoxyresin:curing agent of at least about 1:1, or at least 1.2:1, or even atleast about 1.5:1. In other aspects the weight ratio of epoxyresin:curing agent may be at least about 2:1, and still even at least2.5:1, and even still at least about 3:1.

Also, the components of the curable composition may be mixed anddispersed at a temperature enabling the preparation of an effectivecurable composition having a low viscosity for the desired application.The temperature during the mixing of the components may be from about 0°C. to about 100° C. or from about 0° C. to about 50° C.

Cured Articles

According to another aspect, the curable composition, once formulatedmay be contacted with or applied to any suitable substrate and curedaccording to typical processes practiced by the industry to form a curedarticle. Cured articles in accordance with the present disclosureinclude, but are not limited to, a coating, an adhesive, a constructionproduct, a flooring product, or a composite product.

Typical curing processes include ambient temperature cure to elevatedtemperature cure using thermal, radiation or a combination of energysources. The curable composition may be cured in one step or multiplesteps such as A, B staged cures often practiced in the industries. Or,the curable composition may be post-cured using a different temperatureor energy source after the initial cure cycle.

The temperature at which the curing reaction may be conducted willdepend on the specific epoxy resin and curing agent employed. Thus, inone aspect, the curing temperature may range from about 25° C. to 200°C., or from about 40° C. to about 195° C., or from about 45° C. to about190° C., or from about 50° C. to about 185° C., or from about 60° C. toabout 180° C. or from about 70° C. to about 135° C. In still otheraspects, the curable composition may be cured at a temperature withinthe range of from about 80° C. to about 130° C.

The curable composition may be cured at the previous curing temperaturesfor a time effective to cure the epoxy resin and form the cured article.In some aspects, the curing time may be less than 72 hours. In otheraspects, the curing time may be less than 48 hours, or less than 24hours, or less than 16 hours, or less than 12 hours, or less than 10hours, or less than 8 hours, or less than 6 hours, or less than 4 hoursor less than 2 hours. In still other aspects, the curing time may beless than 60 minutes, or less than 45 minutes or less than 30 minutes.

In one aspect, the curable compositions described above may be used as acoating. For example, a process for forming a coated substrate mayinclude the steps of applying the curable composition to a substrate toform the coated substrate. The curable composition may be applied to thesubstrate by any known technique such as by dipping, spray coating, diecoating, roll coating, resin infusion processes, and contacting thesubstrate with a bath containing the curable composition. Types ofsubstrates that may be coated include, for example, glass, wood,concrete, plastics or polymers that have a relatively high glasstransition temperature (T_(g)) and/or melting point, reinforced fibersand metals. The substrate can be a flat sheet or coil of the desiredmaterial, or may have a more complex profile such as a pipe, tube, wire,or other shape.

In another particular aspect, the curable compositions may be used inindustrial coating applications. Such industrial coatings may includesurface protective coatings applied to substrates that are cured orcrosslinked to form continuous films for decorative purposes as well asto protect the substrate. A protective coating ordinarily comprises anorganic polymeric binder, pigments, and various paint additives, wherethe polymeric binder acts as a fluid vehicle for the pigments andimparts rheological properties to the fluid paint coating. Upon curingor crosslinking, the polymeric binder hardens and functions as a binderfor the pigments and provides adhesion of the dried paint film to thesubstrate. The pigments may be organic or inorganic and may functionallycontribute to opacity and color in addition to durability and hardness.

In further aspects, powder paints may be obtained which comprise thecurable compositions described herein, and suitable pigments, catalystsand additives. These powder paints and coatings therefrom may have asurprisingly good combination of properties. Depending on the choice andthe amount of epoxy resin, curing agent and other optional additives,powder paints derived therefrom may have good flow, good chemicalresistance, high gloss, high scratch resistance, good mechanicalproperties, good outdoor durability and good color stability.

In still other aspects, the curable compositions described herein mayform part of water-based and oil-based dispersions. For example,water-dispersed coating compositions containing the curable compositionsdisclosed herein may be used for can and coil coating compositions.

In still another aspect, the curable composition may be used as anadhesive in methods for bonding one or more substrates together bycontacting one or more surfaces of like or dissimilar substrates to bebonded with the curable composition under conditions sufficient to curethe curable composition including application of pressure and/or heat.

In still further aspects, the curable compositions may also be used inmarine coatings, civil engineering applications, flooring, casting,crack or defect repair, molding, potting, filament winding,encapsulation, and structural and electrical laminates and composites.For example, composites formed using the curable composition disclosedherein may be used in windmill blades and other applications.

In an alternative aspect, the curable composition may be used to producea composite article, such as in castings, prepregs, bonding sheets,laminates and metal-foil clad laminates by techniques well known in theindustry, for example, by pultrusion, infusion, molding, encapsulatingor coating. The properties of the composite articles can be tailored forcertain applications by the addition of reinforced fibers.

Thus, in yet another aspect, there is provided a process for producing acomposite article including the steps of: (i) providing a layer orbundle of reinforced fibers; (ii) providing the curable composition;(iii) contacting the reinforced fibers with the curable composition tocoat and/or impregnate the reinforced fibers; and (iv) curing the coatedand/or impregnated reinforced fibers at a temperature of at least about60° C., or at least about 120° C., or even still at least about 195° C.

EXAMPLES

Examples 1 to 14. Bisphenol a Epoxy Resin (ARALDITE® GY 6010 Epoxyresin) was mixed with a curing agent containing a polyetheramine(JEFFAMINE® D-230 amine), glycerin and a tertiary amine(dimethylaminocyclohexane (DMCHA)) to form a curable composition asshown below in Table 1. Each curable composition was cured at 80° C. forthree hours and then 125° C. for two hours. The glass transitiontemperature of the resulting cured articles was then measured by DSCwith Example 1 serving as the reference. The results below indicate thata tertiary amine catalyst is needed in order to react glycerin into thepolymer backbone. In fact, phase separation was observed when aninsufficient amount of DMCHA was used.

TABLE 1 JEFFAMINE ® Glycerin, ARALDITE ® DMCHA, T_(g), Example D-230, gg GY 6010, g g ° C.  1 6.00 0 18.70 0.00 88.90  2 4.20 0.94 18.70 0.0045.50  3 4.20 0.94 18.70 0.01 46.68  4 4.20 0.94 18.70 0.03 49.15  55.10 0.91 21.32 0.06 71.66  6 5.10 0.91 21.32 0.18 83.55  7 5.40 0.6020.45 0.06 69.48  8 5.40 0.60 20.45 0.18 84.55  9 5.40 0.60 20.45 0.3079.60 10 5.10 0.90 21.32 0.30 80.49 11 4.80 1.20 22.20 0.18 82.98 124.80 1.20 22.20 0.30 82.04 13 5.40 0.61 18.67 0.18 79.66 14 5.10 1.0118.68 0.18 77.57

Examples 15 and 16. Bisphenol A epoxy resin (ARALDITE® GY 6010 epoxyresin) was mixed with a curing agent containing a polyetheramine(JEFFAMINE® D-230 amine), glycerin and a tertiary amine(N-methylmorpholine (NMM)) to form a curable composition as shown belowin Table 2. Each curable composition was cured at 80° C. for three hoursand then 125° C. for two hours. The glass transition temperature of theresulting cured articles was then measured by DSC.

TABLE 2 JEFFAMINE ® Glycerin, ARALDITE ® NMM, T_(g), Example D-230, g gGY 6010, g g ° C. 15 5.40 0.61 20.45 0.18 83.45 16 5.11 0.91 21.32 0.1883.08To compare the properties of the final cured articles, curablecompositions based on Examples 1 (reference), 6 (15% by weightglycerin), and 8 (10% by weight glycerin) were evaluated. The resultsare given below in Table 3.

TABLE 3 Ex. 1 Ex. 6 Ex. 8 Tensile modulus (psi) 408773 438224 419330Tensile strength (psi) 9353 10010 10140 % Elongation at Break 5.04 4.784.97 Flexural modulus (psi) 424682 446175 446408 Flexural strength (psi)14655 15822 15423The results above demonstrate that part of the polyetheramine in thecuring agent may be substituted with glycerin in an epoxy-containingcurable composition without sacrificing the physical properties of thesubsequently cured article.

Although making and using various embodiments of the present inventionhave been described in detail above, it should be appreciated that thepresent invention provides many applicable inventive concepts that canbe embodied in a wide variety of specific contexts. The specificembodiments discussed herein are merely illustrative of specific ways tomake and use the invention, and do not delimit the scope of theinvention.

1-14. (canceled)
 15. A curing agent comprising: (i) from about 65% byweight to about 95% by weight of a polyetheramine selected from thegroup consisting of: a polyether monoamine, a polyether diamine, apolyether triamine, a multifunctional polyetheramine and a mixturethereof; (ii) a tertiary amine having the formula NR₇R₈R₉ where (i) R₇,R₈ and R₉ are independently C₁-C₁₀ alkyl groups or (ii) R₇ and R₈ arejoined as a heterocycloalkyl residue and R₉ is a C₁-C₁₀ alkyl group,wherein the tertiary amine is substantially free of an aromatic tertiaryamine; and (iii) glycerin, where the % by weight is based on the totalweight of the curing agent.
 16. The curing agent of claim 15, whereinthe polyetheramine is a polyether diamine.
 17. The curing agent of claim16, wherein the polyether diamine has the formula (3), (4) or (5):

where c is an integer from about 2 to about 100, H is hydrogen, Me ismethyl and Et is ethyl;

where H is hydrogen, Me is methyl, Et is ethyl, e is an integer fromabout 2 to about 40, and d and f independently are integers from about 1to about 10; or

where g is an integer form about 2 to about
 3. 18. The curing agent ofclaim 15, wherein the polyetheramine is a polyether monoamine having theformula (1) or (1a):

where R is hydrogen, methyl or ethyl, and a and b independently areintegers from about 1 to about 150; or

where Y is hydrogen, methyl or ethyl, Z is a C₁-C₄₀ alkyl group or aC₁-C₄₀ alkyl phenol group, and w is an integer from about 1 to about100.
 19. The curing agent of claim 15, wherein the polyetheramine is apolyether monoamine having the formula (2) or (2a):

where Me is methyl and Et is ethyl.
 20. The curing agent of claim 15,wherein the polyetheramine is a polyether triamine.
 21. The curing agentof claim 15, wherein the polyetheramine is a multifunctionalpolyetheramine having the formula (7):

where each R₄ and R₅ are independently hydrogen or a hydroxyl group,with the proviso that at least one of R₄ is a hydrogen and at least oneof R₅ is a hydroxyl group, Me is methyl and Et is ethyl.
 22. The curingagent of claim 15, wherein the tertiary amine is present in an amountfrom about 0.1% by weight to about 10% by weight, based on the totalweight of the curing agent.
 23. The curing agent of claim 15, whereinglycerin is present in an amount from about 1% by weight to about 25% byweight, based on the total weight of the curing agent.
 24. A curablecomposition comprising: (a) an epoxy resin; and (b) the curing agent ofclaim
 15. 25. The curable composition of claim 24, wherein the epoxyresin is selected from the group of: a polyglycidyl epoxy compound; anon-glycidyl epoxy compound; an epoxy cresol novolac compound; an epoxyphenol novolac compound; and a mixture thereof.
 26. The curablecomposition of claim 25, wherein the epoxy resin is a polyglycidyl epoxycompound.
 27. The curable composition of claim 25, wherein the epoxyresin is a non-glycidyl epoxy compound.
 28. The curable composition ofclaim 24, wherein the curing agent is present in amount of at leastabout 20% by weight, based on the total weight of the curablecomposition.
 29. The curable composition of claim 24, wherein thecurable composition is a 2-package type composition.
 30. A cured articleobtained by applying the curable composition of claim 24 to a substrateand curing the curable composition to form the cured article.
 31. Acurable composition comprising (a) an epoxy resin and (b) a curing agentcomprising: (i) from about 65% by weight to about 95% by weight of apolyetheramine selected from the group consisting of: a polyethermonoamine, a polyether diamine, a polyether triamine, a multifunctionalpolyetheramine and a mixture thereof; (ii) a tertiary amine having theformula NR₇R₈R₉ where (i) R₇, R₈ and R₉ are independently C₁-C₁₀ alkylgroups or (ii) R₇ and R₈ are joined as a heterocycloalkyl residue and R₉is a C₁-C₁₀ alkyl group, wherein the tertiary amine is substantiallyfree of an aromatic tertiary amine; and (iii) glycerin, where the % byweight is based on the total weight of the curing agent and wherein thecurable composition has a ratio of the number of equivalents of reactiveamine hydrogens to the number of equivalents of epoxides of about 0.4 toabout 0.95.
 32. The curable composition of claim 31, wherein the ratioof the number of equivalents of reactive amine hydrogens to the numberof equivalents of epoxides of about 0.5 to about 0.85.
 33. The curablecomposition of claim 32, wherein the ratio of the number of equivalentsof reactive amine hydrogens to the number of equivalents of epoxides ofabout 0.6 to about 0.8.